JP2017206635A - Resin composition and insulated wire using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition having improved abrasion resistance, low temperature flexibility and heat resistance.SOLUTION: A resin composition contains a vinyl chloride resin and dinonyl phthalate. In the resin composition, a reciprocation frequency when an insulated wire in which a conductor having a cross section of 0.3 mmis coated with a resin composition by a thickness of 0.30 mm is subjected to a scraping abrasion test according to JASO D618 is 100 or more. In the resin composition, the conductor is not exposed when the insulated wire is wound around a mandrel having the same diameter as that of the insulated wire under -65°C environment. When the insulated wire which has been heated at 85°C for 3,000 hours is wound around a mandrel having a diameter 1.5 times as the diameter of the insulated wire at 23±5°C environment, the conductor is not exposed.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin composition and an insulated wire using the same. Specifically, the present invention relates to a resin composition that improves wear resistance, low-temperature flexibility and heat resistance, and an insulated wire using the resin composition.

  Since covered wires such as wire harnesses used in automobiles are kept in a high temperature state for a long time in an engine room or the like, they are required to have heat resistance so that the mechanical properties of the material do not deteriorate.

  In addition, with respect to covered electric wires such as wire harnesses used in automobiles, it is required to reduce the thickness of the covering layer that covers the conductors of electric wires as electronic devices become smaller. On the other hand, such a coating layer is required to withstand vibrations of automobiles, and therefore higher wear resistance is required.

  As a resin composition having such heat resistance and wear resistance, conventionally, a thin-walled wear-resistant vinyl chloride resin composition for covering electric wires in which a plasticizer is blended with polyvinyl chloride has been disclosed (for example, Patent Document 1). And this vinyl chloride resin composition is disclosed that a trimellitate plasticizer and a phthalate plasticizer are blended with polyvinyl chloride. Further, it is disclosed that this trimellitate plasticizer has a linear alkyl group having 8 or more carbon atoms, and the phthalate plasticizer has a linear alkyl group having 10 or more carbon atoms.

JP 2013-40268 A

  However, the vinyl chloride resin composition of Patent Document 1 may not have sufficient flexibility under a low temperature environment such as −65 ° C., for example.

  The present invention has been made in view of the problems of such conventional techniques. And the objective of this invention is providing the resin composition which improved heat resistance, abrasion resistance, and low temperature flexibility, and an insulated wire using the same.

The resin composition according to the first aspect of the present invention contains a vinyl chloride resin and dinonyl phthalate. The resin composition is subjected to a scrape abrasion test specified in Japan Automobile Engineers Association Standard JASO D618 on an insulated wire in which a conductor having a cross-sectional area of 0.3 mm ² is coated with a thickness of 0.30 mm. The number of reciprocations when performed is 100 or more. And a resin composition does not have conductor exposure, when an insulated wire is wound around the mandrel of the same diameter as an insulated wire in -65 degreeC environment. When the insulated wire heated at 85 ° C. for 3000 hours is wound around a mandrel having a diameter 1.5 times that of the insulated wire in a 23 ± 5 ° C. environment, there is no conductor exposure.

  The resin composition according to the second aspect of the present invention relates to the resin composition according to the first aspect, wherein the content of dinonyl phthalate is 35 to 60 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.

  The resin composition according to the third aspect of the present invention relates to the resin composition according to the first or second aspect, and the degree of polymerization of the vinyl chloride resin is 1000 to 2500.

  An insulated wire according to a fourth aspect of the present invention includes a coating layer made of the resin composition according to any one of the first to third aspects, and a conductor covered with the coating layer.

  The resin composition according to the embodiment of the present invention contains a vinyl chloride resin and dinonyl phthalate, and the number of reciprocations when a scrape wear test is performed on a predetermined insulated wire is 100 or more. In the resin composition according to the embodiment of the present invention, the conductor is not exposed when the predetermined insulated wire is wound around the predetermined mandrel. Therefore, since the resin composition according to the embodiment of the present invention has wear resistance, low temperature flexibility and heat resistance, it can be suitably used as an insulating material for electric wires.

It is sectional drawing which shows the insulated wire which concerns on embodiment of this invention.

  Hereinafter, a resin composition and an insulated wire according to an embodiment of the present invention will be described in detail with reference to the drawings. In addition, the dimension ratio of drawing is exaggerated on account of description, and may differ from an actual ratio.

[Resin composition]
The resin composition according to this embodiment is mainly composed of a vinyl chloride resin. Vinyl chloride resin is a material that has high heat resistance without being subjected to crosslinking treatment, is excellent in electrical insulation, is inexpensive, and can be easily processed. However, low-temperature flexibility is lowered only with vinyl chloride resin. Therefore, in order to improve the low temperature flexibility, it has been studied to add a plasticizer.

  Known plasticizers for improving the low temperature flexibility include trimellitate plasticizers and phthalate plasticizers. However, even when such a plasticizer is used, sufficient flexibility cannot always be obtained at a low temperature such as −65 ° C.

  Therefore, the resin composition of this embodiment uses dinonyl phthalate as a plasticizer. Dinonyl phthalate is a phthalate plasticizer. When this plasticizer is used, a resin composition excellent in wear resistance, low-temperature flexibility and heat resistance can be obtained.

  Examples of the vinyl chloride resin used in the resin composition of the present embodiment include polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, and vinyl chloride-ethylene copolymer. Polymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride copolymer, vinyl chloride -Styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate copolymer, vinyl chloride-malein Acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride - acrylonitrile copolymer, vinyl chloride - may be mentioned various vinyl ether copolymers. These vinyl chloride resins may be used individually by 1 type, and may be used in combination of 2 or more type. The polymerization method of the vinyl chloride resin is not particularly limited, such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.

  The average degree of polymerization (weight average degree of polymerization) of the vinyl chloride resin is not particularly limited, but is preferably 500 to 5,000. When the average degree of polymerization is 500 or more, it is possible to suppress a decrease in wear resistance of the obtained resin composition. Moreover, when an average polymerization degree is 5000 or less, when extruding a resin composition, the raise of the melt viscosity at the time of extrusion molding can be suppressed, and also the deterioration of kneading | mixing and moldability can be prevented. The average degree of polymerization of the vinyl chloride resin is more preferably 1000 to 2500. When the average degree of polymerization of the vinyl chloride resin is within such a range, a resin composition having good wear resistance and moldability can be obtained. In addition, in the resin composition of this embodiment, you may use the vinyl chloride resin in the range of the said polymerization degree 1 type or in combination of 2 or more types. The average degree of polymerization can be determined according to Japanese Industrial Standards JIS K6720-2: 1999 (Plastics-Vinyl chloride homopolymer and copolymer (PVC)-Part 2: How to make test pieces and various properties).

  As the plasticizer used in the resin composition, dinonyl phthalate (DNP) (CAS registration number 84-76-4) is used. Dinonyl phthalate (DNP) is classified as a phthalate plasticizer. Examples of the plasticizer classified as the same phthalate plasticizer include didecyl phthalate (DDP), di-n-octyl phthalate (DNOP), diisononyl phthalate (DINP), and the like. However, when plasticizers other than dinonyl phthalate are used like these plasticizers, all of the properties of wear resistance, low temperature flexibility and heat resistance cannot be satisfied simultaneously. Therefore, in this embodiment, dinonyl phthalate (DNP) is used as a plasticizer.

  In the resin composition, the content of dinonyl phthalate with respect to 100 parts by mass of the vinyl chloride resin is preferably 35 to 60 parts by mass. When the content of dinonyl phthalate is within this range, the low-temperature flexibility can be improved while suppressing a decrease in wear resistance.

  The resin composition of this embodiment can contain various additives in addition to the above materials. Additives include stabilizers, pigments, antioxidants, extenders, metal deactivators, anti-aging agents, lubricants, fillers, reinforcing agents, UV absorbers, dyes, colorants, antistatic agents, foaming agents, etc. Is mentioned.

  Next, the manufacturing method of the resin composition of this embodiment is demonstrated. The above-mentioned resin composition is prepared by heating and kneading the above-mentioned materials, and known methods can be used for the method. For example, the resin composition can be obtained by kneading the above materials using a known kneader such as a Banbury mixer, a pressure kneader, a kneading extruder, a twin screw extruder, or a roll mill. Alternatively, the above materials may be dry blended in advance using a tumbler or the like and then kneaded using the above kneader. Thus, the resin composition of this embodiment can be obtained by heat-kneading.

In this embodiment, when a scrape wear test specified in JASO D618 is performed on an insulated wire in which a conductor having a cross-sectional area of 0.3 mm ² is coated with the above resin composition at a thickness of 0.30 mm The number of reciprocations is 100 or more. Since the number of reciprocations of the scrape wear test is 100 or more, it has sufficient wear resistance, so that it can be applied to an electrical insulating material for electric wires such as a wire harness. In the scrape wear test, a needle having a diameter of 0.45 ± 0.01 mm can be used. Further, in the scrape wear test, the number of reciprocations of 100 or more means a case where no conduction is established between the metal conductor and the needle having a diameter of 0.45 ± 0.01 mm even when the number of reciprocations is 100 or more.

Furthermore, in the present embodiment, an insulated wire obtained by coating a conductor having a cross-sectional area of 0.3 mm ^{2 with} a resin composition with a thickness of 0.30 mm has the same diameter (diameter 1) as that of the insulated wire in a -65 ° C environment. No conductor exposure when wound around a 3 mm mandrel. Since the conductor of the insulated wire is not exposed under such conditions, it has sufficient low-temperature flexibility, so that it can be applied to an electrical insulating material of a wire such as a wire harness.

In this embodiment, when an insulated wire heated at 85 ° C. for 3000 hours is wound around a mandrel having a diameter 1.5 times that of the insulated wire (diameter 1.95 mm) in an environment of 23 ± 5 ° C. No conductor exposure. In addition, the insulated wire used at this time is the insulated wire which coat | covered the resin composition with the thickness of 0.30 mm to the conductor whose cross-sectional area is 0.3 mm < ² > like the electric wire mentioned above. In such a long-term heating test, since the conductor of the insulated wire is not exposed and has sufficient heat resistance, it can be applied to an electrical insulating material of the wire such as a wire harness.

Thus, the resin composition of this embodiment contains a vinyl chloride resin and dinonyl phthalate. The resin composition is reciprocated when a scrape wear test specified in JASO D618 is performed on an insulated wire in which a conductor having a cross-sectional area of 0.3 mm ² is coated with a thickness of 0.30 mm. The number of times is 100 or more. And when the above-mentioned insulated wire is wound around a mandrel having the same diameter as the insulated wire in a -65 ° C environment, there is no conductor exposure. When the insulated wire heated at 85 ° C. for 3000 hours is wound around a mandrel having a diameter 1.5 times that of the insulated wire in a 23 ± 5 ° C. environment, there is no conductor exposure. Since such a resin composition is excellent in wear resistance and heat resistance in addition to low-temperature flexibility, it can be suitably used as an electrical insulating material for vehicle electric wires.

[Insulated wire]
As shown in FIG. 1, the insulated wire 1 according to this embodiment includes a coating layer 3 made of the resin composition described above and a conductor 2 covered with the coating layer 3.

  As the conductor 2, a single wire constituted by one strand may be used, or a stranded wire constituted by twisting a plurality of strands may be used. A stranded wire is also a concentric stranded wire in which one or several strands are centered and the strands are concentrically twisted around it; a collective stranded wire in which a plurality of strands are twisted together in the same direction; Any composite stranded wire in which a plurality of aggregate stranded wires are twisted concentrically can be used.

  The diameter of the conductor 2 and the diameter of each strand constituting the conductor 2 are not particularly limited. Furthermore, the material of the conductor 2 is not particularly limited, and for example, general metals, conductive fibers, and conductive polymers can be used. In particular, as the material of the conductor 2, known conductive metal materials such as copper, copper alloy, aluminum, and aluminum alloy can be used. These conductive metal materials are particularly preferable because of their good flexibility and conductivity. The surface of the conductor 2 may be plated, for example, tin plating, silver plating, or nickel plating.

  The covering layer 3 covering the outer periphery of the conductor 2 is formed of a resin composition that can ensure electrical insulation with respect to the conductor 2. Specifically, the coating layer 3 is formed of the above resin composition. As described above, the resin composition of this embodiment contains a vinyl chloride resin and dinonyl phthalate, and the number of reciprocations of the scrape wear test under predetermined conditions is 100 or more. Moreover, when the insulated wire is wound around the mandrel under predetermined conditions, there is no conductor exposure. Therefore, it is excellent in wear resistance, low-temperature flexibility and heat resistance, and can be suitably used as an insulating material for electric wires.

  Next, the manufacturing method of the insulated wire 1 of this embodiment is demonstrated. The covering layer 3 of the insulated wire 1 is prepared by heating and kneading the material in the same manner as in the method for producing the resin composition described above. And the method of coat | covering the conductor 2 with the coating layer 3 can also use a well-known means. For example, the coating layer 3 can be formed by a general extrusion method. And as an extruder used by an extrusion molding method, a single screw extruder or a twin screw extruder is used, for example, and what has a screw, a breaker plate, a crosshead, a distributor, a nipple, and a die can be used.

  As a specific method for producing the insulated wire 1, first, a polyvinyl chloride resin composition of the present invention is obtained by preparing a uniform molten mixture according to a conventional method. And this resin composition is used as a resin for insulation coating of electric wires, and the resin composition solidified into a tubular shape by extrusion molding with electric wires (linear conductors formed of conductive metals such as copper wires). An insulating material that becomes an insulator and covers the electric wire is formed. By such a method, an insulated wire in which the wire is covered with an insulating material can be obtained.

  And the wire harness which concerns on this embodiment is provided with the above-mentioned insulated wire 1. FIG. As described above, the insulated wire 1 according to the present embodiment has higher wear resistance, low-temperature flexibility and heat resistance than conventional ones. Therefore, the insulated wire 1 is preferably used for a wire harness that is greatly bent in a short path. be able to.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these Examples.

  First, by using a kneader, the following vinyl chloride resins and plasticizers were melt-kneaded in the blending amounts shown in Table 1 to prepare resin compositions of Examples and Comparative Examples.

(Vinyl chloride resin (PVC))
・ Degree of polymerization 800 S1008 manufactured by Kaneka Corporation
・ Degree of polymerization 1000 S1001 manufactured by Kaneka Corporation
・ Degree of polymerization 1400 Kaneka Corporation S1004
-Degree of polymerization 2500 KS-2500 manufactured by Kaneka Corporation
・ Degree of polymerization 3000 KS-3000 manufactured by Kaneka Corporation

(Plasticizer)
-Polyone Synplast 9P-N made by dinonyl phthalate (DNP) C9 linear type PolyOne Corporation
・ Didecyl phthalate (DDP) C10 linear type Kao Co., Ltd. Vinicizer (registered trademark) 105
・ Di-n-octyl phthalate (DNOP) C8 linear type Kao Co., Ltd. Vinicizer (registered trademark) 85
・ Diisononyl phthalate (DINP) C9 branch type DINP made by J-Plus Co., Ltd.

Next, a pure copper core wire (stranded wire) having a cross-sectional area of 0.3 mm ² (diameter 0.8 mm) was prepared as a metal conductor. And the test which performed extrusion molding on about 180 degreeC temperature conditions using the extrusion coating apparatus for electric wire manufacture which has a screw diameter of 40 mm in diameter with respect to the said metal conductor, and coat | covered with the resin composition of each Example and a comparative example A sample was made. In addition, it adjusted so that the thickness of the coating layer after a coating might be set to 0.30 mm in the case of extrusion molding.

[Evaluation]
About the test sample of an Example and a comparative example, abrasion resistance, low temperature flexibility, heat resistance, and electric wire workability were evaluated by the following method. The results are shown in Table 1.

<Abrasion resistance>
The test samples obtained in the examples and comparative examples were subjected to a wear test in accordance with the scrape wear standard of JASO D618. The conditions for the scrape wear test are as follows.
・ Wear: Needle with a diameter of 0.45 ± 0.01mm ・ Load on test sample: 7 ± 0.05N
・ Needle type: Spring wire (glossy) material ・ Frequency: 55 ± 5 cycles / minute (1 cycle = 1 reciprocating motion)
・ Needle movement: 20 ± 1mm
・ Wear length: 15.5 ± 1 mm
Test temperature: 23 ± 1 ° C
Then, even when the number of reciprocations was 100 times or more, the case where the metal conductor did not conduct between the needle and the needle was evaluated as “◯”, and the case where the reciprocation number was less than 100 was evaluated as “x”.

<Low temperature flexibility>
First, the wire test samples obtained in the examples and comparative examples were cooled in air at −65 ° C. for 4 hours or more. Next, the cooled wire test sample was spirally wound around a metal mandrel (diameter 1.3 mm) having the same diameter as the wire test sample. At this time, the wound electric wire test sample was visually confirmed, the case where the metal conductor was not exposed was evaluated as “◯”, and the case where the metal conductor was exposed was evaluated as “x”.

<Heat resistance>
First, the wire test samples obtained in Examples and Comparative Examples were heated in a gear oven for 3000 hours in an environment of 85 ° C. under an air replacement rate of 8 times / hour. Next, the heated wire test sample was cooled in air at room temperature (23 ± 5 ° C.) for 16 hours or more. Thereafter, the cooled wire test sample was spirally wound around a metal mandrel (diameter 1.95 mm) having a diameter 1.5 times that of the wire test sample. At this time, the wound electric wire test sample was visually confirmed, the case where the metal conductor was not exposed was evaluated as “◯”, and the case where the metal conductor was exposed was evaluated as “x”.

<Electric wire workability>
First, a pure copper core wire having a cross-sectional area of 0.3 mm ² was prepared as a metal conductor. And the resin composition of each Example shown in Table 1 and a comparative example was coat | covered with respect to the said metal conductor using the extrusion coating apparatus for electric wire manufacture which has a diameter of 40 mm. In addition, in the case of extrusion molding, it shape | molded by the preset temperature of an extrusion molding machine at 180 degreeC, and the linear velocity of 300 m / min so that the thickness of the coating layer after a coating might be set to 0.30 mm. The surface of the test sample thus obtained was visually confirmed, and the case where the insulator surface was not rough was evaluated as “◯”, and the case where the insulator surface was rough was evaluated as “x”.

  As shown in Table 1, since Examples 1 to 5 according to this embodiment contain vinyl chloride resin and dinonyl phthalate, it can be seen that they are excellent in wear resistance, low-temperature flexibility and heat resistance. Moreover, since Examples 1-4 which concern on this embodiment are 1000-2500 of the polymerization degree of a vinyl chloride resin, it turns out that it is excellent also in electric wire workability.

  Although the present invention has been described with reference to the examples and comparative examples, the present invention is not limited to these, and various modifications can be made within the scope of the gist of the present invention.

Claims (4)

A resin composition containing a vinyl chloride resin and dinonyl phthalate,
The number of reciprocations when a prescribed scrape wear test in JASO D618 is performed on an insulated wire in which the resin composition is coated with a thickness of 0.30 mm on a conductor having a cross-sectional area of 0.3 mm ² is 100 or more. ,
When the insulated wire is wound around a mandrel having the same diameter as the insulated wire in an environment of −65 ° C., there is no conductor exposure,
Resin composition characterized by having no conductor exposed when the insulated wire heated at 85 ° C. for 3000 hours is wound around a mandrel having a diameter 1.5 times that of the insulated wire in an environment of 23 ± 5 ° C. object.   2. The resin composition according to claim 1, wherein a content of the dinonyl phthalate with respect to 100 parts by mass of the vinyl chloride resin is 35 to 60 parts by mass.   The resin composition according to claim 1 or 2, wherein the degree of polymerization of the vinyl chloride resin is 1000 to 2500. A coating layer comprising the resin composition according to any one of claims 1 to 3,
A conductor coated with the coating layer;
An insulated wire comprising:

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